EP2975081A1 - Nouvelles mousses de polystyrène rigides - Google Patents

Nouvelles mousses de polystyrène rigides Download PDF

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Publication number
EP2975081A1
EP2975081A1 EP15176861.1A EP15176861A EP2975081A1 EP 2975081 A1 EP2975081 A1 EP 2975081A1 EP 15176861 A EP15176861 A EP 15176861A EP 2975081 A1 EP2975081 A1 EP 2975081A1
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Prior art keywords
particles
coal tar
polystyrene
tar pitch
lignite
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German (de)
English (en)
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Wilhelm Frohs
Werner Handl
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SGL Carbon SE
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SGL Carbon SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/224—Surface treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/034—Post-expanding of foam beads or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/036—Use of an organic, non-polymeric compound to impregnate, bind or coat a foam, e.g. fatty acid ester
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • the present invention relates to rigid polystyrene foams comprising green or calcined coal tar coke, lignite coke or mixtures thereof, shaped bodies containing these rigid polystyrene foams and the use of these shaped bodies for thermal insulation.
  • Polystyrene rigid foams have long been known and are used, inter alia, as thermal insulation materials in the form of boards in construction.
  • the rigid polystyrene foam has a closed-cell structure, ie this foam consists to a few percent of solid polystyrene and predominantly of trapped air.
  • This closed-cell structure leads to a low thermal conductivity, which gives the polystyrene foam the good suitability as a thermal insulation material.
  • the density of the polystyrene foam which is determined by the degree of foaming of the polystyrene particles, has a decisive influence on the thermal conductivity.
  • the polystyrene foam used in the construction industry for example, have densities of 20 or 30 kg / m 3 , which corresponds to a thermal conductivity of 40 to 35 mW / m ⁇ K.
  • polystyrene foam with a density of less than 20 kg / m 3 was considered, but this polystyrene foam has too high a thermal conductivity of more than 45 mW / m ⁇ K.
  • Athermane materials are materials that absorb the heat, in particular the heat due to infrared radiation. Accordingly, the addition of athermanous materials reduces the radiopacity of the polystyrene foam.
  • metal oxides for example Al 2 O 3 or Fe 2 O 3
  • non-metal oxides eg SiO 2
  • metal powder aluminum powder, carbon black, graphite, calcined petroleum coke, meta-anthracite, anthracite or organic dyes or dye pigments proposed ( EP 0620246 . WO 97/45477 . WO 98/51734 . WO 00/43442 .
  • an object of the present invention to provide an alternative rigid polystyrene foam containing an athermanous material suitable for thermal insulation which has a density of less than 40 kg / m 3 , preferably less than 20 kg / m 3 and a thermal conductivity of less than 40 mW / m ⁇ K, preferably less than 35 mW / m ⁇ K.
  • the here added athermane material should allow a more energie pioneerere grinding, the milled particles are obtained in the desired platelet shape and these milled particles can also be well dispersed in a polystyrene matrix.
  • the athermane material should not have graphitic structures in order to keep the intrinsic heat conduction low.
  • this object is achieved by a rigid polystyrene foam containing green or calcined coal tar pitch particles, preferably calcined coal tar pitch particles, or lignite coal particles.
  • both the coal tar pitch particles and the lignite coal particles act as athermanous material.
  • mixtures thereof i. a mixture of green and calcined coal tar pitch particles, a mixture of green coal tar pitch and lignite particles, a mixture of calcined coal tar pitch and lignite particles or a mixture of green and calcined coal tar pitch and lignite particles as athermanous material.
  • calcined coal tar pitch particles are particularly preferably used as athermanes material.
  • coal tar pitch particles When referring to coal tar pitch particles hereinafter, it is meant to include both the green and calcined coal tar pitch fuel particles. In the case where either only green or only calcined coal tar pitch fuel particles are meant, in these cases it is explicitly referred to as green or calcined coal tar pitch particles.
  • polystyrene rigid foams comprising brown coal particles and / or coal tar pitch particles have a density of less than 40 kg / m 3 , preferably less than 20 kg / m 3 , and a thermal conductivity of less than 40 mW / m ⁇ K, preferably less than 35 mW / m ⁇ K, ie it is possible to provide the desired thermal insulation properties.
  • both the coal tar pitch and the lignite coal particles can be compared with eg graphite particles (natural graphite or synthetic graphite) energy-efficient grind, since the corresponding throughput is increased, in addition, the proportion of unusable by-product (fine filter dust) compared to graphite is lower.
  • both the milled coal tar pitch particles and the lignite coal particles may be obtained in the desired platelet shape and, compared to graphite particles, these particles are more readily dispersed in the polystyrene matrix because of their surface properties, they better wet the polystyrene matrix and thus better be dispersed. It has surprisingly been found that both the coal tar pitch particles and the lignite coal particles form less agglomerates and therefore require less shear force for homogeneous dispersion. This is particularly advantageous when incorporating these particles in the suspension and / or emulsion polymerization process. In terms of better thermal insulation, it is advantageous that both the coal tar pitch and lignite particles have no graphitic structures, which contributes to lower intrinsic heat conduction.
  • the rigid polystyrene foam may be extruded polystyrene foam (XPS) or polystyrene foam (EPS).
  • XPS extruded polystyrene foam
  • EPS polystyrene foam
  • XPS is produced on extrusion lines as a continuous foam strand;
  • polystyrene is melted in the extruder and, after the addition of a blowing agent, such as CO 2 , continuously discharged through a slot die, which builds behind the slot die the foam strand.
  • foams can be produced with a thickness between 20 and 200 mm.
  • the foam strand is cut to the desired shape, ie into blocks, plates or shaped parts.
  • This extruded polystyrene foam is a closed-cell foam, absorbs only small amounts of moisture and is resistant to aging.
  • XPS is sold under the name Styrodur® C or Styrofoam®.
  • EPS polystyrene granules (polystyrene grit)
  • the blowing agent is copolymerized pentane, pre-expanded at temperatures above 90 ° C. Due to the temperature, the blowing agent evaporates and inflates the thermoplastic base material up to 20 to 50 times to polystyrene foam particles. From these foam particles blocks or plates or molded parts are then prepared in discontinuous or continuous systems by a second hot steam treatment between 110 ° C and 120 ° C.
  • EPS is a predominantly closed-cell insulation material with trapped air, whereby EPS consists of 98% air and is also moisture-resistant.
  • EPS is sold under the name Styropor @.
  • Polystyrene useful for the present invention can be obtained by a suspension polymerization of, for example, styrene in the presence of coal tar pitch or brown coal particles. In this process, the styrene is polymerized in aqueous suspension in the presence of coal tar pitch or lignite particles, and the addition of a propellant, such as pentane, occurs before, during or after the polymerization.
  • styrene is emulsified in water, wherein emulsifiers are used for emulsion stabilization.
  • the initiators used for the polymerization are water-soluble, the polymerization also taking place in the presence of coal tar pitch or lignite particles.
  • Polymers which can be used in the processes described above are expandable styrene polymers, in particular homopolymers and copolymers of styrene, preferably glass-clear polystyrene (GPPS), impact polystyrene (HIPS), anionically polymerized polystyrene or impact polystyrene (A-IPS), styrene-alpha-methylstyrene copolymers , Acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile (SAN) acrylonitrile-styrene-acrylic ester (ASA), methyl acrylate-butadiene-styrene (MBS) and methyl methacrylate-acrylonitrile.
  • GPPS glass-clear polystyrene
  • HIPS impact polystyrene
  • A-IPS anionically polymerized polystyrene or impact polystyren
  • the polystyrene has a weight average M w in the range of 150,000 g / mol to 350,000 g / mol, more preferably from 150,000 g / mol to 300,000 g / mol, most preferably from 180,000 g / mol to 250,000 g / mol.
  • the weight average M w can be determined by gel permeation chromatography at room temperature, with tetrahydrofuran, for example, being used as eluent.
  • both the coal tar pitch particles and the lignite coal particles are homogeneously distributed in the polystyrene foam.
  • this homogeneous distribution of both the coal tar pitch particles and the lignite coal particles in the polystyrene foam (EPS) does not adversely affect the fine cell structure of the styrene polymer particles, in particular the expanded styrene polymer particles, and on the other hand results in improved thermal insulation properties of the polymer foam produced. Consequently, neither the coal tar pitch particles nor the lignite coke particles interfere with nucleation in the production of, for example, EPS.
  • This homogeneous distribution of the coal tar pitch particles as well as the brown coal particles is also aided by the good dispersibility of these particles in the polystyrene matrix. Due to the surface properties of these particles, they can be well wetted by the polystyrene matrix, which in the dispersion ensures that the agglomerates are better divided, ie. There are fewer total agglomerates in the polystyrene matrix.
  • both the coal tar pitch particles and the lignite coal particles are used platelet-shaped.
  • the platelet form of these particles likewise does not impair the fine cell structure of the styrene polymer particles, in particular of the expanded styrene polymer particles; on the other hand, the platelets have a larger surface, for example compared to the spherical shape, as a result of which these platelets have a highly reflective effect on the incident infrared radiation.
  • both the coal tar pitch and lignite particles have an aspect ratio greater than 2, preferably greater than 10, more preferably greater than 20.
  • these aspect ratios are in the range of greater than 2 to 20, more preferably in the range of greater than 10 to 50, and most preferably in the range of greater than 20 to 100.
  • the circle diameter (D) of the surface of the wafer is added to the thickness (T ) of the platelet, as in FIG. 1 will be shown.
  • the incident infrared radiation is reflected particularly well.
  • the good reflection of the infrared radiation requires that this radiation is only slightly absorbed, which means that, for example, moldings produced from the rigid polystyrene foam according to the invention do not heat up strongly under sunlight and are thus not deformed.
  • the Steinkohlenteerpechkoksteilchen or Braunkohlenkoksteilchen a diameter d 50 from 0.2 to 20.0 microns, more preferably from 0.5 to 15.0 microns, most preferably from 1.0 to 10, 0 ⁇ m, most preferably from 4.0 to 8.0 ⁇ m.
  • the d 50 value indicates the average particle size, with 50% of the particles being smaller than the stated value.
  • the d 10 value of these particles is preferably 0.1 to 5.0 ⁇ m, particularly preferably 0.2 ⁇ m to 4.0 ⁇ m, and most preferably 0.5 ⁇ m to 3.0 ⁇ m; the d 98 value of these particles preferably prefers 15.0 to 25.0 ⁇ m, more preferably 16.0 to 23.0 ⁇ m. Below the d 10 value or the d 98 value It is understood that 10% of the particles or 98% of the particles are smaller than the specified value.
  • the coal tar pitch or lignite particles have a d 10 value of 0.5 to 3.0 ⁇ m, a d 50 value of 4.0 to 8.0 ⁇ m and a d 98 value of 16.0 to 23.0 microns have.
  • Coal tar which is used for the production of coal tar coke, is produced as a by-product in the production of metallurgical or coal coke by the coking of coking coal from coke oven coking ovens (coking plants) at a temperature of more than 1000 ° C.
  • coal tar attracts about 4 to 5 weight percent (wt.%) Based on the feed weight of the coking coal.
  • this pitch serves as raw material feed for the so-called "delayed coker”.
  • green coal tar coke is obtained by coking coal tar pitch at a temperature of about 480 ° C.
  • This coking process of delayed coking is a thermal process known from the mineral oil industry to convert heavy distillation and crack residues into gasoline and diesel.
  • other coking processes such as chamber coking or coking in retorts, can also be used to produce green coal tar coke.
  • this green coal tar coke is calcined in a subsequent step at a temperature of 1100 ° C to 1500 ° C to drive off residual volatiles, calcined coal tar coke is obtained.
  • This calcination can be done in a rotary kiln calciner, turntable calciner or even in a vertical shaft calciner.
  • calcined coal tar pea cokes and / or calcined (semi) isotropic coal tar pitch cokes are used as the preferred calcined coal tar pitch cokes. It is also possible a mixture semi-isotropic and isotropic coal tar coke, or a mixture of calcined coal tar peel coke, semi-isotropic and isotropic coal tar coke.
  • the calcined coal tar pea cokes preferably have a coefficient of thermal expansion (CTE) of 0.0 - 0.3 x 10 -6 K -1
  • the semi-isotropic coal tar pitch coke preferably has a CTE of 2.0 to 3.5 x 10 -6 K -1
  • the calcined isotropic coal tar pitch coke prefers a CTE of 3.5 to 5.5 x 10 -6 K -1 .
  • Lignite coke can be produced by the coking of lignite, this coking can be done basically in all industrially used stove and chamber furnaces, rotary kilns or turntable ovens.
  • the coking temperatures in this case can be in a range from 800 ° C. to 1400 ° C., preferably from 1200 ° C.
  • Green and calcined coal tar pitch cokes or lignite cokes used according to the invention can be characterized as follows: lignite Steinkohleteerpechkoks CTE [10 -6 K -1 ] 0.00 - 5.5 Bulk density [g / cm 3 ] 0,70 - 1,00 Hydrogen content [% by weight] 0.20 - 0.40 0.035 - 0.150 Nitrogen content [% by weight] 0.05-0.40 0,30 - 2,00 Sulfur content [% by weight] 0.28 - 1.00 0.15-0.60 Ash content [% by weight] 2,00 - 13,50 0.02-0.60 Carbon content [% by weight]: 85.00 - 97.50 96.70 - 99.50
  • the measurement of the CTE corresponds to DIN 51909, the sample preparation DIN 51930.
  • the helium density is in accordance with DIN 51915, the bulk density according to DIN 51916, the hydrogen, nitrogen and sulfur content according to DIN 51372 and the ash content according to DIN 51903.
  • the determination of the carbon content results arithmetically.
  • lignite coke is characterized by its comparatively high specific surface area. This is greater than 50 m 2 / g and can reach up to 500 m 2 / g (measured according to ASTM D 3037/89). By activation, this specific surface can be increased up to 1000 m 2 / g.
  • the polystyrene foam comprises carbon coal pitch or lignite particles in an amount of from 0.5% to 10.0% by weight, preferably from 1.0% to 8.0% by weight. -%, more preferably from 2.0 wt .-% to 6.0 wt .-%, most preferably from 3.0 wt .-% to 5.5 wt .-% based on the amount of rigid foam.
  • polystyrene foams containing mixtures of green or calcined coal tar pitch particles, for blends of green coal tar pitch and lignite particles, for blends of calcined coal tar pitch and lignite particles, or blends of green and calcined coal tar pitch and lignite particles.
  • polystyrene rigid foams contain these mixtures in an amount of from 0.5% by weight to 10.0% by weight, preferably from 1.0% by weight to 8.0% by weight, particularly preferably 2.0% by weight .-% to 6.0 wt .-%, most preferably from 3.0 wt .-% to 5.5 wt .-% based on the amount of rigid foam.
  • coal tar pitch and / or lignite coal particles is further advantageous in that the particles are obtained after milling in the desired platelet form.
  • grinding jet mills can be selected from the group consisting of air, gas or steam jet mills be used.
  • the preferred air jet mill used is a spiral jet or counter jet mill, particularly preferably a spiral jet or counter jet mill comprising an integrated separator.
  • the particles to be ground are accelerated so that the forces acting on the particles enable a direction-dependent comminution, ie there are tensile and frictional forces as well as particle collisions, which lead to a desired comminution of the particles as well as a preferred particle shape
  • the millbase can also be fed to an external classifier to obtain particularly steep particle size distribution curves, ie coarser and finer particles can be well separated from each other by this measure an even more precise upper or lower grain boundary can be performed.
  • the rigid polystyrene foams are used as thermal insulation materials in the form of boards in construction, it is necessary that these insulating materials are flame retardant, ie they pass the fire tests B1 and B2 according to DIN 4102.
  • the polystyrene rigid foams according to the invention are not easily flammable and the required fire tests
  • the rigid foams may additionally contain flame retardants. These flame retardants are organic halogen compounds, preferably organic bromine compounds, particularly preferably aliphatic, cycloaliphatic or aromatic bromine compounds, and / or phosphorus compounds.
  • organic bromine compounds from the group consisting of hexabromocyclododecane, pentabromochlorocyclohexane or pentabromophenyl allyl ether, and phosphoric compounds being particularly preferred 9, 10-Dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOP-O) or triphenyl phosphate (TPP).
  • DOP-O 10-Dihydro-9-oxa-10-phospha-phenanthrene-10-oxide
  • TPP triphenyl phosphate
  • the required amount of flame retardant can be reduced, ie the flame retardants are in the polystyrene foam in an amount of less than 2.0 wt .-%, preferably less than 1.5 wt .-%, particularly preferably less than 1.0% by weight, based on the amount of rigid foam.
  • the polystyrene foam according to the invention can be produced cheaper and more environmentally friendly, since less flame retardants, in particular less organic bromine compounds and / or phosphorus compounds are needed.
  • a more cost-effective production of the rigid polystyrene foam according to the invention is also made possible in that the rigid foam has a density of 1 to 20 kg / m 3 , preferably from 5 to 20 kg / m 3 , more preferably from 10 to 20 kg / m 3 and most preferably from 12 to 18 kg / m 3 .
  • the rigid foam has a density of 1 to 20 kg / m 3 , preferably from 5 to 20 kg / m 3 , more preferably from 10 to 20 kg / m 3 and most preferably from 12 to 18 kg / m 3 .
  • it comes to a material saving since less polystyrene can be used.
  • the rigid polystyrene foam according to the invention has a thermal conductivity of from 20 mW / mK to 40 mW / mK, preferably from 25 mW / mK to 35 mW / mK.
  • the present invention furthermore relates to a shaped body which contains a rigid polystyrene foam according to the invention and to the use of such a shaped body for thermal insulation.
  • a shaped body for example, plates can be considered, which are used for thermal insulation, preferably in construction.
  • a styrene polymer having an average molecular weight from 180,000 to 250,000 g / mol and a melt index of 4.8 cm 3/10 min. (ISO1133) with 1.9 wt .-% hexabromocyclododecane (HBCD) and 7 wt .-% pentane mixture (consisting of n-pentane, iso-pentane and cyclopentane) was melted in a co-rotating twin-screw extruder and by means of a sidefeeder with 4 wt. % milled coal tar coal fired.
  • HBCD hexabromocyclododecane
  • pentane mixture consisting of n-pentane, iso-pentane and cyclopentane
  • the used coal tar coke was ground in a spiral jet mill with integrated classifier and had a mean particle size d 50 of 7 ⁇ m (d 98 of 21 ⁇ m, d 10 of 1 ⁇ m).
  • the polymer melt mixed with the stated additives was processed into EPS granules by means of an underwater granulator having an outlet pressure of 9 bar.
  • commercial anticaking agents such as calcium stearate were sprinkled and then foamed in a batch prefoamer to a density 16 kg / m 3 .
  • To measure plates were cut out, conditioned and examined for thermal conductivity according to DIN 4102. The measurement showed a thermal conductivity of 31.0 mW / m K.
  • a styrene polymer having an average molecular weight from 150,000 to 350,000 g / mol and a melt index of 14 cm 3/10 min (ISO 1133) with 2.0 wt .-% HBCD and 6 wt .-% Penta mixture was melted in a corotating twin screws and on the Feeding charged with 4.5 wt .-% milled coal tar puffed coke.
  • the coal tar coke was milled with a hot gas-powered spiral jet mill and completely freed of fine dust by means of a separate high-performance sifter.
  • the milled coal tar coal coke had a mean particle size d 50 of 6 ⁇ m (d 98 of 18 ⁇ m, d 10 of 2 .mu.m).
  • the processing was carried out according to Example 1.
  • the plates had a density of 15 kg / m 3 after foaming and conditioning.
  • the measured thermal conductivity according to DIN 4102 gave a value of 30.5 mW / mK.
  • Example 2 4.5% by weight ground coal tar coke was added without changing the polymer, additive and extrusion conditions.
  • the coal tar coke was milled to the following parameters in a countercurrent grinder powered by a gas-fired countercurrent grinder, the ground coal tar coke having a mean particle size d 50 of 5 ⁇ m (d 98 of 17 ⁇ m, d 10 of 1.5 ⁇ m).
  • the panels produced had a density of 15 kg / m 3 after foaming and conditioning.
  • the measured thermal conductivity according to DIN 4102 gave a value of 32.5 mW / mK.
  • a styrene polymer having an average molecular weight from 180,000 to 250,000 g / mol and a melt index of 4.8 cm 3/10 min. (ISO1133) with 1.9 wt .-% hexabromocyclododecane (HBCD) and 7 wt .-% pentane mixture (consisting of n-pentane, iso-pentane and cyclopentane) was melted in a co-rotating twin-screw extruder and by means of a sidefeeder with 4 wt. % milled lignite coke applied.
  • HBCD hexabromocyclododecane
  • pentane mixture consisting of n-pentane, iso-pentane and cyclopentane
  • the used lignite coke was ground in a spiral jet mill with integrated classifier and had a mean particle size d 50 of 5 ⁇ m (d 98 of 20 ⁇ m, d 10 of 1 ⁇ m).
  • the polymer melt mixed with the stated additives was processed into EPS granules by means of an underwater granulator having an outlet pressure of 9 bar.
  • commercial anticaking agents such as calcium stearate were applied and then foamed in a batch prefoamer to a density of 16 kg / m 3 .
  • To measure plates were cut out, conditioned and examined for thermal conductivity according to DIN 4102. The measurement showed a thermal conductivity of 31.5 mW / mK.

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP15176861.1A 2014-07-15 2015-07-15 Nouvelles mousses de polystyrène rigides Withdrawn EP2975081A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620246A1 (fr) 1993-04-13 1994-10-19 ALGOSTAT GmbH & CO. KG Pièces moulées en mousse de polystyrène rigide
WO1997045477A1 (fr) 1996-05-28 1997-12-04 Basf Aktiengesellschaft Polymerisats de styrene expansibles contenant des particules de noir de fumee
WO1998051734A1 (fr) 1997-05-14 1998-11-19 Basf Aktiengesellschaft Procede de production de polymerisats de styrene expansibles contenant des particules de graphite
WO2000043442A1 (fr) 1999-01-25 2000-07-27 Sunpor Kunststoff Ges.Mbh Polymeres de styrene particulaires, expansibles, et leur procede de production
WO2010031537A1 (fr) 2008-09-17 2010-03-25 H.C. Carbon Gmbh Corps, en particulier corps moulé en polystyrène
DE202010013851U1 (de) 2010-08-27 2010-12-16 Sunpor Kunststoff Gesellschaft M.B.H. Flammgeschützte, expandierbare Polymerisate
DE202010013850U1 (de) 2010-08-27 2010-12-16 Sunpor Kunststoff Gesellschaft M.B.H. Polymerschaumkörper oder teilchenförmige expandierbare Polymerisatpartikel
US20110046249A1 (en) * 2008-05-07 2011-02-24 Polimeri Europa S.P.A. Compositions of expandable vinyl aromatic polymers with an improved thermal insulation capacity, process for their preparation and expanded articles obtained therefrom
US20110284793A1 (en) * 2008-12-19 2011-11-24 Polimeri Europa S.P.A. Compositions of expandable vinyl aromatic polymers with an improved thermal insulation capacity, process for their production and expanded articles obtained therefrom

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2953999A1 (fr) * 2013-02-05 2015-12-16 SGL Carbon SE Mousses de polystyrène

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620246A1 (fr) 1993-04-13 1994-10-19 ALGOSTAT GmbH & CO. KG Pièces moulées en mousse de polystyrène rigide
WO1997045477A1 (fr) 1996-05-28 1997-12-04 Basf Aktiengesellschaft Polymerisats de styrene expansibles contenant des particules de noir de fumee
WO1998051734A1 (fr) 1997-05-14 1998-11-19 Basf Aktiengesellschaft Procede de production de polymerisats de styrene expansibles contenant des particules de graphite
WO2000043442A1 (fr) 1999-01-25 2000-07-27 Sunpor Kunststoff Ges.Mbh Polymeres de styrene particulaires, expansibles, et leur procede de production
US20110046249A1 (en) * 2008-05-07 2011-02-24 Polimeri Europa S.P.A. Compositions of expandable vinyl aromatic polymers with an improved thermal insulation capacity, process for their preparation and expanded articles obtained therefrom
WO2010031537A1 (fr) 2008-09-17 2010-03-25 H.C. Carbon Gmbh Corps, en particulier corps moulé en polystyrène
US20110284793A1 (en) * 2008-12-19 2011-11-24 Polimeri Europa S.P.A. Compositions of expandable vinyl aromatic polymers with an improved thermal insulation capacity, process for their production and expanded articles obtained therefrom
DE202010013851U1 (de) 2010-08-27 2010-12-16 Sunpor Kunststoff Gesellschaft M.B.H. Flammgeschützte, expandierbare Polymerisate
DE202010013850U1 (de) 2010-08-27 2010-12-16 Sunpor Kunststoff Gesellschaft M.B.H. Polymerschaumkörper oder teilchenförmige expandierbare Polymerisatpartikel

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